Composition containing modified wax



J Patented Feb. 8, 1944 UNIT STATES COMPOSITION co ng' smmc Momma!) Eugene Lieber, West New Brighton, Staten Island, N. Y., assignor to Standard Oil Development Company, a corporation of Delaware I No Drawing.

f 13Claims.

This invention relates to improved compositions containing a hydrocarbon wax and contain- Application November 1, 1939, Serial No. 302,320

ing a wax-modifying agent and more particular- 1y to such a wax-modifying agentyvhen used as a pour depressor in lubricating oils, as well as to an improved method of preparing such wax-modifying agents. J

Broadly, the-invention comprises polymerizing halogeno alkyl aromatic hydrocarbons under controlled conditions to produce .a light to viscous 011, recovering from said product a high molecular weight residue by distillation, preferably with fire and steam, and incorporatingthe resultant oil-soluble residue, which is found to have surprising wax-modifying properties, into a compo-- sition containing a hydrocarbon wax. The raw material to be polymerized may be a compound having the following general formula in which Ris selected from the group consisting of aromatic hydrocarbons and halogen deriva- 'tives thereof, R is a saturated aliphatic hydroof halogen present in the alkyl group corresponds to one atom of halogen to one mol of alkyl aromatics. If such compounds are not readily available," they may be prepared by halogenating the alkyl aromatic hydrocarbon under conditions tending to produce chlorination only in the. alkyl group rather than on the aromatic nucleus In carrying out the halogenation, it is preferred to use chlorine because it is both effective and readily available at low cost. However, if desired, other halogens may be employed, such as bromine, iodine .or fluorine.- Generally, this chlorination should be carried out until about 5 to 25% of chlorine has been combined into the alkyl groupof the alkyl aromatic compounds. In practice, it is found that chlorination to a content of 'Z to 12% of chlorine gives results which are sub- "zstantially superior to those obtainable with other chlorine contents. After the chlorination of the alkyl aromatic compound has been completed, the product is refined in such a war as to recover all of the compounds-in which thefhalogen is incorporated essentially in the alkyl group. If

desired, this product; which will'usually consist of a mixture of specific compounds in which chlorine atoms are attached to various carbon atoms of the alkyl group, may be subjected to As to the halogen, it is believedthat the best results are obtainable when the amount.

some fractionation treatment such'as distillation,

precipitation, etc., in order to recover separately any one or more of the compounds.

In carrying out the polymerization step, a FriedeL-Crafts type catalyst is used, preferably aluminum chloride, and this should be preferably anhydrous. Other catalysts of this type include ferric chloride, boron fluoride, zinc chloride, titanium tetrachlorid and thelike. The reaction involved here is called polymerization because there is only a single reactant, namely, the halogeno alkyl aromatic hydrocarbon compound. However, it is believed that the reaction actually involves some condensation to the extent that at least part of the chlorine incorporated in the side chains of the alkyl aromatic compounds combine with a hydrogen atom of an adjacent molecule and the two are liberated together as hydrogen chloride. Usually about I to 20% of aluminum chloride is used but preferably the amount should be between the narrower limits of about 5% to 15% but surprisingly superior results are obtained by using 10% and therefore this particular amount is preferred.

.During the polymerization, it is preferred to use an inert solvent or diluent, which should preferably be present in an amount corre'sponding to somewhere between about 50%. and. 500%- of the weight of the halogeno alkyl aromatic hydrocarbons to be polymerized.

which usually proceeds vigorously is permitted quantity of inert diluent and then the residual catalyst is inactivated by neutralizing with a mixture of water and alcohol. After removal of r the aqueous layer by settling, centrifuging or able as a pour depressor, i. e., a material whichother suitable means, the upper or kerosene layer isdistilled to remove low-boiling'products, and to leave a residue which is usually a resinous mass, which is the wax-modifying agent of this invention.

This product has been found particularly suitdepresses or lowers the pour point of a lubricating oil (which is artificially determinedv at 5 F.

The reaction above the temperature at which the oil becomes this wax modifier, will lower the pour point of an oil which normally has a pour point at-30? 1''. down to 5 F. or even far below F. such as -25 F., the potency of the product being dependent upon the specific conditions used in the polymerization. When used as an addition agent to lubricating oil, the product of this invention has additional advantages such as that of imparting a greenish bloom and a deep red through color characteristic of Pennsylvania type oils.

Although it is primarily intended to use this wax modifier as a pour depressor in lubricating oils, it is also useful as an aid for settling, filtering or centrifuging a wax such as from a solution of hydrocarbon wax and an oil in a diluent such as naphtha,- as used in dewaxing processes. For

. such a purpose, about 1% to of the wax modiden is used, based upon the estimated amount of wax which is to be separated from the iubricating oil.

The wax modifier of thisinvention is also suit- 'able for improving the texture of wax, such as parailln wax to be used for coating paper, etc, in which case the amount of waxmodifler to be used should usually be within the range of about 1% to 30% in the total composition of wax and wax modifier, preferably between the narrower limits of about 5% to As examples of alkyl aromatic compounds which can be used a starting materials for the chlorination, thejollowing may serve as repre- I sentative:

- Propyl benzene"; V

CsHsCaHv Butyl benzene Calls-C43: Amyl benzene CcHs-CsHu Octyl benzene CcHs-CaHrl Di-amyl benzene CsHs-(CsHu):

Instead of using plain alk'yl aromatic compounds, one may also use halogen-substituted derivatives thereof, e.. g., chlorinated compounds such as di-chlor amyl benzene having the for- 1111118, CeHflCDz-CaHu. A180, of plain aromatic compounds with a single aromatic nucleus, dior even poly-nuclear compounds may be used such as alphaor beta-butyl naphthalene,

alpha-amy] naphthalene, di-amyl naphthalene,

etc. Furthermore, although the alkyl aromatic compounds and their substituted derivatives, as

- mentioned above, are preferred, chiefly due to the pound,.such as mono-amyl naphthalene, was I chlorinated by passing chlorine through the hydrocarbon, maintained at about 200 to 225 F. The chlorination proceeded readily at this temperature to give a light-colored product and was continued until about by weight of chlorine had been absorbed. 170 grams of the resulting chloro-arnyl naphthalene were dissolved in 150 cc. of kerosene (made inert by treating with alusolid). Forinstance,asshowninthe datalater,

K the addition of a small amoimt such as 2% ofmlnumchloride prior to use) and 8.5 grams of aluminum chloride were added thereto while agitating at room temperature. The reaction proceeded readily as evidenced by the vigorous evoluresinous mass was obtained as a bottom residue,

which is the wax modifier of the present invention. To test the pour depressor characteristics of this material, a small amount, such as 2% or 5%, is dissolved in a lubricating oil having a known pour point, such as F. (This is a pour point characteristic of a good grade Pennsylvaniatype oil after the usual dewaxing.)

Tablei Plou rphi am Rawmatenal Mat 30 A101: Yicld DIM Name 01 2%- Percent Percent Percent l 15 5 71 6 10 2 15 i0 69 0 -20 3 15 20 I -1O 4 23 5 54 0 25 5 E1 10 22 25 6 9.1 15 51 -10 '7 18.9 10 27 10 8 9.3 l0 18 25 40 s as 15 a5 5 i0 22 5 27 -10 -30 I 1 Based on weight of chlorinatedsromatic raw material used.

9 The lube oil bass stock used in making the pour point tests had a poor point of +3) I".

lubricating oil, imparted a greenish bloom and a deep red through color to it which is characteristic of Pennsylvania type oils. .In test #1 the 9 product was a dark green resinous mass. The

1 product of test #2 had a similar appearance. In

' test #3 tetrachlorethane was used as' solvent inreaction temperature at 68 F. then the reaction stead of kerosene and the 34 grams of anhydrous .AlCl: were added slowly over a period of minutes with suitable agitation and maintaining the temperature was increased to 212 F. and maintained thereafter for 60 minutes. The product of test #3 when added to pale lubricating oil even at concentrations below 0.5% was found to import a pleasing green bloom and fluorescence as well as a deep through red color to the oil. The product of test #3 wasfa dark brown resinous mass. The product of test #4 was a black resinous substance, which was found to be a powerful lubricating oil dye for pale oils. The product of test #5 was a black resinous substance. The product of test #7 was a black resinous substance which was'also found to impart a greenish fiuorescence and deep red through color to pale oils. The product oftest #8 was also a black'resinous material. In test #10 a kerosene fraction of petroleum was used which had an aniline point of F. and the product obtained was a dark is green resinous substance.

The product of test #1 when blended in a pale In the appended claims, the word all zy is intended to meana saturated aliphatic hydrocarbon group.

It is not intended that this invention be limited by any theory suggested as to the mechanism of the operation of the. invention nor by any of the specific examples which have been given only for the sake of illustration, but only by the appended claims in which it is intended to claim all novelty inherent in the invention as broadly as the prior art permits.

I claim:

1. A composition comprising a hydrocarbon wax and an oil-soluble wax-modifying agent comprising an auto-condensation product of a compound having the following general formula: RR'X, in which R is a compound selected from the group consisting of aromatic hydrocarbons and halogen derivatives thereof, R is a saturated aliphatic hydrocarbon group containing less than carbon atoms, and X represents one or more halogen atoms in the aliphatic'group R.

2. A composition according to claim 1 in which the wax modifier is a residue obtained by fire and steam distillation to 600 F.

3. A composition according to claim 1 in which the wax modifier is an auto-condensation product of a chlor-alkyl naphthalene.

4. A composition according to claim 1 in which the wax modifier is an auto-condensation product of a chlor-alkyl benzene.

5. -A composition comprising a hydrocarbon wax and a wax-modifying agent consisting essentially of an auto-condensation product of a chloramyl derivative of an aromatic. hydrocarbon having less than 3 nuclei.

6. A lubricant comprising an oil containing dissolved waxy constituents which normally tend to prevent pouring of the oil at low temperatures, and also containing a small amount of a poor depressor comprising essentially an auto-condensation product of a halogen alkyl cyclic hydrocarbon having not more than 10 alkyl carbon atoms.

7. The method of preparing improved wax-containing compositions which comprises subjecting about 7% to 12% chlorine and the resultant wax modifier into a composition comprising a hydrocarbon wax.

8. The method of preparing improved wax-containing compositions which comprises chlorinating an alkylated cyclic hydrocarbon having not more than 10 alkyl carbon atoms to about 5% to 25% chlorine essentially in the alkyl group and subjecting to auto-condensation the. resultant chlorinated hydrocarbon with about 1% to 20% of a Friedel-Crafts catalyst to make a product of light to viscous oil consistency, separating from said product a wax modifier residue and incorporating said wax modifier into a composition comprising a wax-containing lubricant.

9. Method according to claim 8 in which an alkylated aromatic hydrocarbon is chlorinated to chlorinated alkylated aromatic hydrocarbon is subjected to auto-condensation with about 5% to 15% of aluminum chloride at room temperature until the reaction begins to slow down and then raising the temperature to about 150-250 F. for about an hour. v

10, Method according to claim 8 in which an amyl derivative of an aromatic hydrocarbon having less than 3 nuclei is chlorinated to about 9% chlorine and the resultant chlor-amyl aromatic compound is subjected to auto-condensation with about 10% of aluminum chloride.

11. The method of making lubricants which comprises chlorinating an allq lated cyclic hydrocarbon having not more than 10 alkyl carbon atoms to about 5% to 25% chlorine essentially in the alkyl group and polymerizing the resultant chlorinated hydrocarbon with about 1% to 20% of a Friedel-Crafts catalyst to make a product of light to viscous oil consistency, separating from said product a wax modifier residue and incorporating said wax modifier into a composition comprising a wax-containing 1ubricant.

12. A lubricant comprising a major proportion of a waxy mineral lubricating oil containing dis solved therein a small amount of a pour depressor to auto-condensationa halogeno alkyl cyclic hydrocarbon having not more than 10nlkylcarbon atoms with a Friedel-Crafts catalyst under conditions to make a product of light to viscous oil consistency, separating from said product a wax modifier residue obtainable by fire and steam distillation to about 600 F., and incorporating said consisting of a product substantially non-volatile up to about 600 F. under fire and steam distilla'- tion and obtained by the Friedel-Crafts autocondensation of a chlorinated alkyl aromatic hydrocarbon containing about 5% to 25% of chlorine and having not more than 10 alkyl carbon atoms.

' 13. Lubricant according to claim 12, in which the pour depressor is derived by auto-condensa- 

